CN102983333A - Novel preparation method of lithium vanadium phosphate/carbon composite material for positive pole of lithium ion battery - Google Patents
Novel preparation method of lithium vanadium phosphate/carbon composite material for positive pole of lithium ion battery Download PDFInfo
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- CN102983333A CN102983333A CN2012105477234A CN201210547723A CN102983333A CN 102983333 A CN102983333 A CN 102983333A CN 2012105477234 A CN2012105477234 A CN 2012105477234A CN 201210547723 A CN201210547723 A CN 201210547723A CN 102983333 A CN102983333 A CN 102983333A
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- lithium
- composite material
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Abstract
The invention discloses a novel preparation method of a lithium vanadium phosphate/carbon composite material for a positive pole of a lithium ion battery. The novel preparation method comprises the following steps of: uniformly diffusing a lithium source compound, a vanadium source compound and a phosphorus source compound according to a stoichiometric ratio, and adding a chelating agent with a proper ratio; forming black blue mash at a certain temperature after a certain time period; drying and uniformly grinding the mash; preheating the mash in a muffle furnace at the certain temperature; and roasting in a non-oxide atmosphere at a temperature of 500-900 DEG C for 2-48 hours; and slowly cooling to a room temperature, so as to obtain Li3V2(PO4)3 particles. According to the novel preparation method provided by the invention, the Li3V2(PO4)3 material is synthesized by using a water-soluble reduction method, so that the material prepared in a liquid mixing manner has high purity; and the specific capacity of the material is greatly improved, and the cycle life of the material can be greatly prolonged as a conductive carbon network uniformly covers the surfaces of particles.
Description
Technical field
The present invention relates to a kind of novel preparation method of lithium ion cell positive vanadium phosphate lithium/carbon composite material, particularly relate to a kind of method for preparing the material presoma with aqueous solution.The vanadium phosphate lithium/carbon composite material synthetic with the method has preferably cycle performance and charge/discharge capacity.
Background technology
Lithium ion battery take new forms of energy and new material technology as background since energy density high, have extended cycle life, the advantage such as self discharge is little, be widely used in the information industries such as mobile phone, notebook computer, and expanded to gradually electric automobile, peak load regulation network, solar power station electric power storage equal energy source field of traffic.The research Showed Very Brisk of anode material for lithium-ion batteries, comparatively commonly with transition metal oxide as positive electrode, such as LiCoO
2, LiNiO
2And LiMn
2O
4Deng.LiCoO
2Commercialization, but its selling at exorbitant prices, toxicity is larger; LiNiO
2Synthetic relatively difficulty; LiMn
2O
4Then exist theoretical capacity low, the shortcoming that cycle performance is relatively poor.Therefore, the exploitation of novel anode material is the inexorable trend of lithium ion battery development.Contain polyanion (PO
4)
3-Anode material for lithium-ion batteries be subject to more and more widely paying close attention to.The Li of monocline
3V
2(PO
4)
3Between 3-4.8V, can reversiblely take off 3 lithium ions of embedding, theoretical specific capacity is 197mAhg
-1Because PO
4 3-Substituted the position of oxygen atom, so that structure is more stable, thus Li
3V
2(PO
4)
3Has good cycle performance.Add that the vanadium source is abundant, cheap, so Li
3V
2(PO
4)
3Has researching value.
The synthetic method of phosphoric acid vanadium lithium mainly contains high temperature solid-state method, carbothermic method, microwave sintering method and sol-gal process at present.High temperature solid-state method technique is simple, easily industrialization, but generated time purity long, synthetic sample is not high, particle diameter is large, chemical property is relatively poor; Though carbothermic method can reduce cost and improve material property, the tap density of meeting imaging material.It is short that microwave method has the reaction time, the advantage that energy consumption is low, but heating uniformity is wayward, product purity can not guarantee that chemical property is relatively poor.The sol-gal process synthesis temperature is lower, product cut size is little, chemical property is better, but often needs to consume a large amount of chelating agents, and process is comparatively complicated.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing lithium ion cell positive vanadium phosphate lithium/carbon composite material with aqueous solution.The material for preparing and traditional high temperature solid-state method, sol-gel process, the methods such as spray drying process are compared, and the method has good dispersion, and purity is high, dissolving is abundant, and grain diameter is even, and step is few, save raw material, produce effective, the various features that the reaction time lacks.
Technical scheme of the present invention is summarized as follows:
Prepare the novel method of lithium ion cell positive vanadium phosphate lithium/carbon composite material with aqueous solution, may further comprise the steps:
(1) with vanadium source compound, Li source compound and P source compound according to Li
3V
2(PO
4)
3The stoichiometric proportion weighing, and be dissolved in the solvent;
(2) mol ratio according to chelating agent and vanadium is weighing in 1: 20～10: 1, is dissolved in the solvent, and mixes with composite material, stirs at a certain temperature and forms black-and-blue pastel;
(3) with grinding evenly after the pastel vacuumize in (2), place preheating under the Muffle furnace uniform temperature;
(4) after the sample after the preheating ground, compressing tablet placed 500～900 ℃ of lower roasting 2～48h of nonoxidizing atmosphere, slowly is down to room temperature, obtains Li
3V
2(PO
4)
3Particle.
Described vanadium source compound comprises VOC
2O
4, VO
2, V
2O
5, NH
4VO
3In one or more mixing.
Described Li source compound comprises one or more the mixing in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium iodide, lithium bromide, LiBF4, the lithium oxalate.
Described P source compound comprises one or more the mixing in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, the phosphorus pentoxide.
Described solvent comprises one or more in water, ethanol, methyl alcohol, the acetone.
Described chelating agent comprises one or more the mixing in ethylenediamine tetra-acetic acid (EDTA), citric acid, tartaric acid, the polyethylene glycol.
Described preheat temperature is 300 ℃-400 ℃, and the heat treated time is 3-4h;
Described nonoxidizing atmosphere comprises the mixed atmosphere of nitrogen, argon gas, hydrogen and argon gas.
The present invention adopts emphatically aqueous solution that phosphoric acid vanadium lithium/carbon composite anode material presoma is studied.The method is to utilize the heating for dissolving combination in water of lithium source, vanadium source, phosphorus source, carbon source, according to the color of the solution reaction, determines that redox reaction must occur in its inside, and has gas to emerge.Solution is by yellow (V
5+) finally to become blue pastel (may be V
4+, also may be V
3+, V
4+Mixture, also may be V
3+, V
4+, V
5+Mixture).The method need not be crossed multiprocessing in course of reaction, avoid regulating with ammoniacal liquor in the sol-gel process process of pH value.The Li of the method preparation
3V
2(PO
4)
3Particle surface can form the conductive carbon network, and material electronics conductivity obviously improves, and has good chemical property.
Description of drawings
Fig. 1 is embodiment 1 preparation Li
3V
2(PO
4)
3The XRD collection of illustrative plates of sample.
Fig. 2 is embodiment 1 preparation Li
3V
2(PO
4)
3The FESEM figure of sample.
Fig. 3 is embodiment 1 preparation Li
3V
2(PO
4)
3The first charge-discharge curve chart of sample.
Fig. 4 is embodiment 1 preparation Li
3V
2(PO
4)
3The cycle performance figure of sample.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments, and unrestricted the present invention:
Embodiment 1
Take lithium carbonate, vanadic oxide, ammonium dihydrogen phosphate as raw material, according to the stoichiometric proportion weighing, be dissolved in the deionized water.Take citric acid as chelating agent, according to citric acid: V=1: 1 ratio weighing, and soluble in water.After mentioned solution mixes, at 80 ℃ of lower 10h that stir, form gel.Wet gel is put into air dry oven behind 110 ℃ of lower dry 12h, obtain xerogel.Pack into after the grinding in the tube furnace, under High Purity Nitrogen atmosphere in 600 ℃ of constant temperature 10h.Obtain Li after the cooling
3V
2(PO
4)
3Particle.The crystal structure of gained sample is tested with Rigaku D/MAX-RC type x-ray diffractometer, and test condition is Cu Ka radiation, graphite monochromator, surface sweeping scope 2 θ=10～80 °, 8 °/min of sweep speed.Adopt the NEC JSM-6490LV of company type electron microscope, to the size of sample particle, pattern and distribution are observed.Fig. 1 is the XRD collection of illustrative plates of the sample of embodiment 1 preparation.Mark the index of main peaks among the figure, gone out peak position and monocline Li
3V
2(PO
4)
3XRD result coincide, sample purity is higher.Can find out that according to Fig. 2 this sample particle is evenly distributed, shape is more consistent, slightly reunites.Particle surface has continuous conductive carbon network.With Li
3V
2(PO
4)
3, conductive black, PTFE 85: 10: 5 ratio in mass ratio, add an amount of ethanol and mix, stir into bulk, making thickness is 0.1mm and smooth uniform thin slice, is pressed in 120 ℃ of lower vacuumize 12h on the aluminium foil with tablet press machine, does anodal for subsequent use.Make negative pole with metal lithium sheet, microporous polypropylene membrane (Celgard 2400) is as barrier film, and with the LiPF of 1mol/L
6DC/DMC solution (volume ratio is 1: 1) be electrolyte solution, in the argon gas glove box, assemble simulated battery.The charge-discharge performance test is carried out with the emerging PCBT-32D-D multi-pore channel of Wuhan power battery controlled testing instrument.Test voltage scope 3.0-4.3V.Fig. 3 is the first charge-discharge curve chart of prepared material in the test voltage scope.Sample is with the 0.1C rate charge-discharge, first discharge capacity 128mAhg
-1, with theoretical capacity 132mAhg
-1Comparatively approaching.
Embodiment 2
P source compound among the embodiment 1 substitutes with ammonium phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, and other conditions remain unchanged.
Embodiment 3
Lithium carbonate among the embodiment 1 substitutes with lithium hydroxide, lithium acetate, lithium nitrate, lithium iodide, lithium bromide, LiBF4, lithium oxalate etc., and other conditions remain unchanged.
Embodiment 4
Chelating agent among the embodiment 1 substitutes with ethylenediamine tetra-acetic acid (EDTA), tartaric acid, polyethylene glycol etc., and other conditions remain unchanged.
Claims (8)
1. the novel preparation method of a lithium ion cell positive vanadium phosphate lithium/carbon composite material is characterized in that, may further comprise the steps:
(1) with vanadium source compound, Li source compound and P source compound according to Li
3V
2(PO
4)
3The stoichiometric proportion weighing, and be dissolved in the solvent;
(2) mol ratio according to chelating agent and vanadium is weighing in 1: 20～10: 1, is dissolved in the solvent, and mixes with composite material, stirs at a certain temperature and forms black-and-blue pastel;
(3) with grinding evenly after the pastel vacuumize in (2), place preheating under the Muffle furnace uniform temperature;
(4) after the sample after the preheating ground, compressing tablet placed 500～900 ℃ of lower roasting 2～48h of nonoxidizing atmosphere, slowly is down to room temperature, obtains Li
3V
2(PO
4)
3Particle.
2. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1 is characterized in that, described vanadium source compound comprises VOC
2O
4, VO
2, V
2O
5, NH
4VO
3In one or more mixing.
3. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1, it is characterized in that described Li source compound comprises one or more the mixing in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium iodide, lithium bromide, LiBF4, the lithium oxalate.
4. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1, it is characterized in that described P source compound comprises one or more the mixing in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, the phosphorus pentoxide.
5. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1 is characterized in that, described solvent comprises one or more in water, ethanol, methyl alcohol, the acetone.
6. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1, it is characterized in that described chelating agent comprises one or more the mixing in ethylenediamine tetra-acetic acid (EDTA), citric acid, tartaric acid, the polyethylene glycol.
7. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1 is characterized in that, described preheat temperature is 300 ℃-400 ℃, and the heat treated time is 3-4h.
8. the novel preparation method of a kind of lithium ion cell positive vanadium phosphate lithium/carbon composite material according to claim 1 is characterized in that, described nonoxidizing atmosphere comprises the mixed atmosphere of nitrogen, argon gas, hydrogen and argon gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682276A (en) * | 2013-12-24 | 2014-03-26 | 中南大学 | Preparation method for cathode material LiVOPO4/C adopting sheet structure for lithium ion battery |
| CN106711411A (en) * | 2016-12-07 | 2017-05-24 | 深圳市沃特玛电池有限公司 | Preparation method of lithium iron phosphate/carbon composite material |
| CN108054349A (en) * | 2017-11-10 | 2018-05-18 | 江汉大学 | A kind of carbon coating type phosphoric acid vanadium lithium and preparation method thereof |
| CN114094082A (en) * | 2021-11-22 | 2022-02-25 | 湖南裕能新能源电池材料股份有限公司 | Lithium vanadium phosphate-carbon composite cathode material, preparation method thereof, lithium ion battery and electric equipment |
-
2012
- 2012-12-17 CN CN2012105477234A patent/CN102983333A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682276A (en) * | 2013-12-24 | 2014-03-26 | 中南大学 | Preparation method for cathode material LiVOPO4/C adopting sheet structure for lithium ion battery |
| CN103682276B (en) * | 2013-12-24 | 2015-12-30 | 中南大学 | The preparation method of laminated structure lithium ion battery positive pole material phosphoric acid vanadyl lithium/carbon |
| CN106711411A (en) * | 2016-12-07 | 2017-05-24 | 深圳市沃特玛电池有限公司 | Preparation method of lithium iron phosphate/carbon composite material |
| CN108054349A (en) * | 2017-11-10 | 2018-05-18 | 江汉大学 | A kind of carbon coating type phosphoric acid vanadium lithium and preparation method thereof |
| CN114094082A (en) * | 2021-11-22 | 2022-02-25 | 湖南裕能新能源电池材料股份有限公司 | Lithium vanadium phosphate-carbon composite cathode material, preparation method thereof, lithium ion battery and electric equipment |
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Application publication date: 20130320 |